Wieghardt et al, in JACS, 110, 7398 (1988) describe the synthesis of [MnIV2(μ-O)3(Me3-TACN)2](PF6)2 by reacting a dinuclear bis-carboxylate bridged Me3-TACN manganese (III) complex in ethanol/water mixture and air (dioxygen) (Me3-TACN=1,4,7-trimethyl-1,4,7-triazacyclononane).
Wieghardt et al, in JACS, 120, 13104 (1998) describe the synthesis of [MnIVMnIII(μ-O)2(μ-OAc)(Me4-DTNE)](ClO4)2 by reacting Mn(III) acetate in methanol and allow slow aerial oxidation to form the complex (Me4-DTNE=1,2-bis-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane).
Koek et al., in Inorg Chim Acta, 295, 189 (1999) describe the synthesis of dinuclear Mn(IV) complexes based on TACN derivatives using water/ethanol mixtures.
WO96/06154 describes the synthesis of [MnIVMnIII(μ-O)2(μ-OAc)(Me4-DTNE)](PF6)2 by reacting Mn(II) acetate tetrahydrate in ethanol/water in the presence of KPF6, after which hydrogen peroxide/NaOH was added and subsequently neutralised using acetic acid.
WO2006/125517 discloses the preparation in aqueous media and use of manganese complexes with 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me3-TACN) and 1,2-bis-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane (Me4-DTNE) as highly-water soluble salts in bleaching.
U.S. Pat. No. 5,274,147, to Unilever, discloses the formation of tri-mu-oxo bridged manganese complexes containing Me3-TACN carried by treatment of dinuclear bis-carboxylate bridged complexes in aqueous ethanol solutions.
U.S. Pat. No. 5,153,161, to Unilever, discloses the formation of tri-mu-oxo bridged manganese complexes containing Me3-TACN carried by treatment of aqueous solutions of ligand with manganese salts and hydrogen peroxide.
U.S. Pat. No. 5,256,779, to Unilever, discloses the formation of tri-mu-oxo bridged manganese complexes containing Me3-TACN carried by treatment of aqueous solutions of ligand with manganese salts and hydrogen peroxide.
WO 2005/033070, to BASF, discloses the addition of an aqueous solution of Mn(II)acetate to an aqueous solution of Me3-TACN followed by addition of a organic substrate followed by addition of hydrogen peroxide.